CN102190822A - Tire rubber composition and heavy-load tire - Google Patents
Tire rubber composition and heavy-load tire Download PDFInfo
- Publication number
- CN102190822A CN102190822A CN2011100404459A CN201110040445A CN102190822A CN 102190822 A CN102190822 A CN 102190822A CN 2011100404459 A CN2011100404459 A CN 2011100404459A CN 201110040445 A CN201110040445 A CN 201110040445A CN 102190822 A CN102190822 A CN 102190822A
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- Prior art keywords
- rubber
- tire
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- mass parts
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- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000035602 clotting Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 125000000000 cycloalkoxy group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 125000005070 decynyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C#C* 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- NBBQQQJUOYRZCA-UHFFFAOYSA-N diethoxymethylsilane Chemical compound CCOC([SiH3])OCC NBBQQQJUOYRZCA-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- XYYQWMDBQFSCPB-UHFFFAOYSA-N dimethoxymethylsilane Chemical compound COC([SiH3])OC XYYQWMDBQFSCPB-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000005879 dioxolanyl group Chemical group 0.000 description 1
- ZVDBUOGYYYNMQI-UHFFFAOYSA-N dodec-1-yne Chemical compound CCCCCCCCCCC#C ZVDBUOGYYYNMQI-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WYMSENKWVCCQGJ-UHFFFAOYSA-N n,n-dimethyl-1-triethoxysilylmethanamine Chemical compound CCO[Si](CN(C)C)(OCC)OCC WYMSENKWVCCQGJ-UHFFFAOYSA-N 0.000 description 1
- DFVIRQNGJPSMQP-UHFFFAOYSA-N n,n-dimethyl-1-trimethoxysilylmethanamine Chemical compound CO[Si](OC)(OC)CN(C)C DFVIRQNGJPSMQP-UHFFFAOYSA-N 0.000 description 1
- XTOSZDRAGWRSBP-UHFFFAOYSA-N n,n-dimethyl-2-triethoxysilylethanamine Chemical compound CCO[Si](OCC)(OCC)CCN(C)C XTOSZDRAGWRSBP-UHFFFAOYSA-N 0.000 description 1
- RKOBOSOXEJGFTF-UHFFFAOYSA-N n,n-dimethyl-2-trimethoxysilylethanamine Chemical compound CO[Si](OC)(OC)CCN(C)C RKOBOSOXEJGFTF-UHFFFAOYSA-N 0.000 description 1
- QVUHBALXLZYVMB-UHFFFAOYSA-N n,n-dimethyl-4-triethoxysilylbutan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCCN(C)C QVUHBALXLZYVMB-UHFFFAOYSA-N 0.000 description 1
- UWUDIBKKKUZPQH-UHFFFAOYSA-N n,n-dimethyl-4-trimethoxysilylbutan-1-amine Chemical compound CO[Si](OC)(OC)CCCCN(C)C UWUDIBKKKUZPQH-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- KPIIDEIURMTGCD-UHFFFAOYSA-N n-ethyl-n-(trimethoxysilylmethyl)ethanamine Chemical compound CCN(CC)C[Si](OC)(OC)OC KPIIDEIURMTGCD-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- OSSQSXOTMIGBCF-UHFFFAOYSA-N non-1-yne Chemical group CCCCCCCC#C OSSQSXOTMIGBCF-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- HZIVRQOIUMAXID-UHFFFAOYSA-N oxocane Chemical compound C1CCCOCCC1 HZIVRQOIUMAXID-UHFFFAOYSA-N 0.000 description 1
- YVQBOKCDPCUWSP-UHFFFAOYSA-N oxonane Chemical compound C1CCCCOCCC1 YVQBOKCDPCUWSP-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical class Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C1/00—Treatment of rubber latex
- C08C1/02—Chemical or physical treatment of rubber latex before or during concentration
- C08C1/04—Purifying; Deproteinising
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/25—Incorporating silicon atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
- C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
Abstract
The present invention provides: a rubber composition for a tire that achieves both good fuel economy and abrasion resistance, and also achieves good degradation resistance and processability; and a heavy-load tire having a tread produced therefrom. The present invention relates to a rubber composition for a tire, comprising a rubber component that contains a modified natural rubber having a phosphorus content of 200 ppm or less and a butadiene rubber, wherein the amount of the modified natural rubber is 60 to 95% by mass and the amount of the butadiene rubber is 5 to 40% by mass, based on 100% by mass of the rubber component.
Description
Technical field
The present invention relates to rubber composition for tire, and use this rubber combination to be used for the heavy duty tire of tyre surface.
Background technology
In recent years, the formulation of the increase of fuel cost and environmental planning has increased the demand of improving the car industry fuel economy.In fuel-economy, be used for producing the rubber combination that accounts for the tyre surface of tire significant proportion at various tyre elements and require very outstanding.
Known as well-known improvement method in the fuel economy is the method that reduces filler such as sooty content.Yet the minimizing of filler content tends to cause the reduction of rubbery intensity and the deterioration of wear resistance.Therefore, it is very difficult making fuel economy and wear resistance both reach very high level.In rubber combination, the same with wear resistance with fuel economy, anti-degradation property has become a requirement.Therefore need a kind of method can obtain good fuel economy and wear resistance, keep good anti-degradation property simultaneously.
The elastoprene of modification is used in patent documentation 1-3 suggestion, reduces rolling resistance such as modification divinyl rubber and styrene-butadiene rubber(SBR).Patent documentation 4 and 5 suggestions have been removed protein-free natural rubber by use and have been improved rubbery intensity.Yet, require to realize that fuel economy and wear resistance all reach higher level, the space of improving of keeping the good resistance degradation property simultaneously still exists.
About tire (especially heavy duty tire), the method for using natural rubber or divinyl rubber to become rubber components is the ordinary method that is used to improve fuel-economy.The known silicon-dioxide that is to use of method that further improves fuel-economy is as the method for filler and the method for minimizing filler content.Yet these methods may reduce rubbery intensity and can not keep good wear resistance.Especially, be used for the high rubbery intensity of rubber combination needs of heavy duty tire, therefore be difficult to aforesaid method is applied to these rubber combinations.In addition, tend to such as increasing the viscosity when mixing and reduce scorch time with silane coupling agent commonly used that silicon-dioxide is united use, thereby may cause the side effect on the processibility.Therefore, need a kind of fuel economy, wear resistance and workability of making to reach the balanced method of improving.
Patent documentation 6 has disclosed a kind of rubber combination, and it is used to increase the content of non-petroleum sources by using the preparation of natural rubber and epoxy natural rubber.Yet this rubber combination still has obtains the balanced space of improving of fuel economy, wear resistance and processibility.
Patent documentation 1:JP 2001-114939A
Patent documentation 2:JP 2005-126604A
Patent documentation 3:JP 2005-325206A
Patent documentation 4:JP H08-12814A
Patent documentation 5:JP H11-12306A
Patent documentation 6:JP 2007-169431A
Summary of the invention
The object of the invention provides a kind of rubber composition for tire, and this rubber combination can address the above problem so that both reached good fuel economy and wear resistance, reaches good degradation resistant and workability again.The present invention also aims to provide a kind of tire with tyre surface of producing by this rubber combination.
The present invention relates to a kind of rubber composition for tire, it comprises a kind of rubber components, it is following modified natural rubber and divinyl rubber of 200ppm that this rubber components comprises phosphorus content, wherein, rubber components with 100 quality % is a benchmark, and the content of modified natural rubber is that the content of 60-95 quality % and divinyl rubber is 5-40 quality %.
Preferably below the 20 quality %, gel content is confirmed as the substances content of insoluble toluene to the gel content of modified natural rubber.
Modified natural rubber is preferably at its chloroform extract
31During measuring, P NMR do not contain-3 phosphatide peaks to the 1ppm scope, so that it does not contain phosphatide substantially.
Modified natural rubber preferably comprises the following nitrogen of 0.3 quality %.
Modified natural rubber preferably is generated by the saponification natural rubber latex.
Divinyl rubber is the modification divinyl rubber preferably.
Divinyl rubber is compound modified by shown in the formula (1) preferably:
R wherein
1, R
2And R
3Be same or different, each in them is all represented alkyl, alkoxyl group, silyloxy, acetal radical, carboxyl, sulfydryl or their derivative; R
4And R
5Be same or different, each in them is all represented hydrogen atom, alkyl or cyclic ethers base, and n represents integer.
Divinyl rubber is preferably synthetic with rare earth catalyst.
With the preferred cis-content of rare earth catalyst synthetic divinyl rubber is more than the 95 quality % and contents of ethylene is below the 1.0 quality %.
Rubber combination preferably further comprises: silicon-dioxide and silane coupling agent, wherein silane coupling agent is the multipolymer that comprises the unit B shown in unit A shown in the formula (2) and the formula (3), and the ratio that unit B accounts for unit A and unit B mole total amount is 1 to 70 mole of %, and the content of silicon-dioxide is 10 to 60 mass parts in per 100 mass parts rubber components:
Wherein, x and y each all be integer more than 1; R
6Represent hydrogen, halogen, side chain or unbranched C
1-30Alkyl or alkylidene group, side chain or unbranched C
2-30Alkenyl or alkylene group (alkenylene), side chain or unbranched C
2-30Alkynyl or alkynylene (alkynylene) or the group that obtains by terminal hydrogen with hydroxyl or carboxyl substituted alkyl or alkenyl; R
7Represent hydrogen, side chain or unbranched C
1-30Alkylidene group or alkyl, side chain or unbranched
C2-30Alkylene group (alkenylene) or alkenyl or side chain or unbranched C
2-30Alkynylene (alkynylene) or alkynyl, and R
6And R
7Can form ring texture together.
Rubber combination preferably further comprises carbon black.
Rubber combination is preferred for the heavy duty tire tyre surface.
The present invention also relates to a kind of heavy duty tire, this tire comprises the tyre surface of being produced by rubber combination.
According to the present invention, rubber composition for tire comprises rubber components, and this rubber components comprises the modified natural rubber that contains carbamate additives for low phosphorus and the divinyl rubber of predetermined content.Therefore, the purposes that rubber combination is used for the heavy duty tire tyre surface provides a kind of heavy duty tire, and this tire both can be obtained good fuel economy and wear resistance, can obtain good degradation resistant and workability again.
Embodiment
Rubber composition for tire of the present invention comprises modified natural rubber (HPNR) and the divinyl rubber (BR) that contains carbamate additives for low phosphorus.Compare with the use of natural rubber (NR), the use that comprises on a small quantity or do not comprise the modified natural rubber (HPNR) of protein among the NR, gel content and phosphatide can impel the further improvement of fuel-economy.In addition, the reduction of mooney viscosity can obtain good processibility.Yet, in HPNR synthetic, removed the degradation resistant composition among the NR by NR saponification or similar processing.The degraded that this can cause rubber in early days causes the reduction of performance such as anti-degradation property and wear resistance.Otherwise, since the present invention used common HPNR with BR as rubber components, fuel economy and wear resistance can both improve, and these two property can both successfully obtain.In addition, thus also can keep good anti-degradation property makes fuel-economy type, wear resistance and anti-degradation property reach balanced to improve.Further, can also obtain good workability.
Modified natural rubber (HPNR) has the following phosphorus content of 200ppm.The above phosphorus content of 200ppm tends to cause the increase of storage stage gel content and the increase of vulcanizate compositions tan δ.Below the preferred 150ppm of phosphorus content, be more preferably below the 100ppm.Here, phosphorus content can be measured such as the ICP emission spectrometry by the method for routine.Phosphorus derives from phosphatide (phosphorus compound).
Modified natural rubber preferably has the following gel content of 20 quality %, is more preferably the following gel content of 10 quality %, most preferably is the following gel contents of 7 quality %.The above gel content of 20 quality % tends to cause the reduction of processibility, as the increase of mooney viscosity.Gel content is meant the content of measuring as a kind of material that is insoluble to toluene (a kind of non-polar solvent).Hereinafter, this content also abbreviates " gel content " or " gel component " as.Gel content is measured by following method: at first, the natural rubber sample is immersed in the dehydrated toluene, it is rested on dark place one week prevented irradiate light.Next, toluene solution is with 1.3 * 10
5The speed of rpm is by centrifugal 30 minutes, so that be insoluble to the gel component of toluene and be dissolved in the component of toluene disconnected from each other.Be insoluble to the gel component of toluene and methanol mixed so that be cured, dry then.At last, gel content is determined according to the ratio of the quality of the quality of exsiccant gel component and initial sample.
Modified natural rubber does not preferably contain phosphatide substantially.Herein, term " does not contain phosphatide " and refers at the extract that obtains by chloroform extraction natural rubber sample substantially
31During detecting, P NMR do not have-3 the existence at phosphatide peak to the scope of 1ppm.The peak of phosphate ester structure during the phosphatide peak that exists in-3 to 1ppm scopes refers to corresponding to the phosphorus composition of phosphatide.
Modified natural rubber preferably contains the following nitrogen of 0.3 quality %, is more preferably the following nitrogen of 0.15 quality %.If the content of nitrogen surpasses 0.3 quality %, the tendency that causes that Mooney intensity increases between the shelf lives is arranged then.Nitrogen source is in albumen.Can determine nitrogen content such as triumphant formula nitriding by ordinary method.
Modified natural rubber is such as can preparing the resultant rubber that is solidified of saponification reaction after scouring, the rubber after the dry then washing by the method with the alkali soap natural rubber latex.Saponification reaction is by adding alkali and optional tensio-active agent to natural rubber latex and make mixture leave standstill the regular hour under predetermined temperature to carry out.Herein, mixture can randomly be stirred or stand other operation.This preparation method can remove P contained compound, isolates phosphorus compound by washing in saponification reaction, thereby can reduce the phosphorus content in the natural rubber.In addition, therefore the protein in the saponification reaction degraded natural rubber can reduce the nitrogen content in the natural rubber.In the present invention, can to natural rubber latex, carry out saponification reaction, and be added in the natural rubber latex and preferably can cause effective saponification reaction by adding alkali.
Natural rubber latex is the juice that extracts from Hevea, comprises composition for example water, protein, lipid and inorganic salt and rubber components.Gel component is considered to derive from the mixture of the plurality of impurities in the rubber in the rubber.Being used for latex of the present invention can be the lactogenesis glue that obtains by from the Hevea rubber tapping, perhaps by the centrifugal purifying latex that is concentrated.Selectively, high ammonia latex can be used, and it is to add ammonia by a kind of common method to be produced to the untreated rubber latex, so that suppress owing to be present in the caused untreated rubber latex of bacterium in the latex and addle and prevent solidifying of latex.
The example that is used for the alkali of saponification reaction comprises sodium hydroxide, potassium hydroxide, calcium hydroxide and aminated compounds.In these compounds, sodium hydroxide and potassium hydroxide are particularly preferred, are used for the good saponification and the stability of natural rubber latex.
The addition of alkali is not particularly limited.Based on the solid in per 100 mass parts natural rubber latexes, the minimum addition of alkali preferably more than 0.1 mass parts, is more preferably more than 0.3 mass parts.Based on the solid in per 100 mass parts natural rubber latexes, the maximum addition of alkali preferably below 12 mass parts, is more preferably below 10 mass parts, below further preferred 7 mass parts, below preferred especially 5 mass parts.The addition of alkali may cause long saponification reaction less than 0.1 mass parts.On the other hand, the addition of alkali may make the natural rubber latex instability greater than 12 mass parts.
The tensio-active agent that uses can be anionic surfactant, nonionic surface active agent or amphoterics.The anionic surfactant example comprises carboxylate ion tensio-active agent, sulfonate ion tensio-active agent, sulfate ion tensio-active agent and phosphate ion tensio-active agent.The nonionic surface active agent example comprises polyoxyalkylene ether nonionic surface active agent, polyoxyalkylene esters nonionic surface active agent, polyhydric alcohol fatty acid ester nonionic surface active agent, saccharide fatty acid ester nonionic surface active agent and APG (alkylpolyglycoside) nonionic surface active agent.The amphoterics example comprises amino acid amphoteric surface activator, betaine amphoteric surface activator and amine oxide amphoteric surface activator.In these tensio-active agents, preferred anionic type surfactant is more preferably sulfonate anionic type surfactant.
Based on the solid in per 100 mass parts natural rubber latexes, more than preferred 0.01 mass parts of the minimum addition of tensio-active agent, be more preferably more than 0.1 mass parts, further more than preferred 1.1 mass parts and more than preferred especially 2.0 mass parts.Based on the solid in per 100 mass parts natural rubber latexes, below preferred 6.0 mass parts of the maximum addition of tensio-active agent, be more preferably below 5.0 mass parts, further below preferred 3.5 mass parts and below preferred especially 3.0 mass parts.The addition of tensio-active agent may cause natural rubber latex instability during the saponification reaction less than 0.01 mass parts.On the other hand, the addition of tensio-active agent may be stablized natural rubber latex excessively greater than 6.0 mass parts, makes that latex is difficult to solidify.Addition is phosphorus content, nitrogen content and the gel content that can further reduce more than 1.1 mass parts in the natural rubber.
Temperature during the saponification reaction can suitably be set in the following scope: allow to carry out saponification reaction with alkali with enough speed of reaction, and can not cause that the natural rubber latex sex change for example solidifies.Usually, preferably 20 to 70 ℃ of the temperature during the saponification reaction are more preferably 30 to 70 ℃.In the situation that allows natural rubber latex to leave standstill, preferably 3 to 48 hours saponification reaction time cycle, be more preferably 3 to 24 hours, be used for the enough saponification reactions and the improvement of productive rate, though it depends on the temperature during the saponification reaction.
After saponification reaction, solidify, and smash the rubber that is solidified, then washing.The example of clotting method comprise with acid for example formic acid be added into latex so that regulate the method for latex pH.The example of washing methods comprises the method that rubber after solidifying with the water dilution of washing usefulness and centrifugal mixture extract rubber.Before centrifugal, at first carry out water dilution, so that be 5 to 40 quality % by the rubber content that forms in the natural rubber latex, and preferred 10 to 30 quality %.Then, diluted rubber stock can be also with 5000 to 10000rpm speed by centrifugal 1 to 60 minute, and such washing can carry out having up to rubber to be obtained the phosphorus content of expection continuously.After washing is finished, can generate the natural rubber latex of handling through saponification.Then, the natural rubber latex of handling through saponification is dried, so that obtain the natural rubber that is modified according to of the present invention.
In this production method, saponification, washing and drying preferably are extracted in back 15 days at natural rubber latex and finish.In addition, being more preferably at latex was extracted in back 10 days, further preferably finished saponification, washing and drying in 5 day.This is that then gel content can increase because if latex leaves standstill and surpasses 15 days and be not cured after extraction.
In rubber combination of the present invention, the content of modified natural rubber is more than the 60 quality % in the rubber components of 100 quality %, more than the preferred 65 quality %, is more preferably more than the 68 quality %.The content of modified natural rubber may not substantially improve fuel economy less than 60 quality %.The content of modified natural rubber is below the 95 quality % in the rubber components of 100 quality %, below the preferred 92 quality %.The content of modified natural rubber can provide than the BR of small proportion greater than 95 quality % and wear resistance be arranged and the tendency of degradation resistant deterioration.
Rubber combination of the present invention can comprise BR.BR is not particularly limited, and its example comprises the BR of high-cis content and contains the polyhutadiene crystalline BR of syndiotaxy (syndiotactic).Other example comprises the BR that obtains by with the polymerization catalyst that comprises group of the lanthanides row rare earth compound, as such as disclosed in JP2003-514078T.In the middle of these examples, the BR with high-cis content is preferred.
The preferred example of BR comprises the divinyl rubber (being called " modification BR ") with modifier modification.Utilize modification BR can reduce the Tg (second-order transition temperature) of polymkeric substance and improve for example dispersity of carbon black of weighting agent.The result is that degradation resistant can improve fuel economy and wear resistance simultaneously keeping preferably.The preferred example of modification BR comprises with divinyl rubber compound modified shown in the above-mentioned formula (1) (being called " S-modification BR ").
In the compound shown in the above-mentioned formula (1), R
1, R
2And R
3Be same or different, each in them is all represented alkyl, alkoxyl group, first silica (silyloxy) base, acetal radical, carboxyl, and (COOH), sulfydryl (SH) or their derivative.
Examples of alkyl groups comprises C
1-4Alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl and the tertiary butyl for example.
The alkoxyl group example comprises C
1-8(preferred C
1-6, be more preferably C
1-4) alkoxyl group for example methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy and tert.-butoxy.The alkoxyl group example comprises that also cycloalkyloxy is (such as C
5-8Cycloalkyloxy is the hexamethylene alkoxyl group for example) and aryloxy (such as C
6-8Aryloxy is phenoxy group and benzyloxy for example).
The silyloxy example comprises by C
1-20The silyloxy (for example trimethylammonium silyloxy, silicoheptane oxygen base, triisopropyl silyloxy, diethyl sec.-propyl silyloxy, tertiary butyl dimethyl methyl siloxy, tert-butyl diphenyl silyloxy, tribenzyl silyloxy, triphenyl silyloxy and three pairs of methylbenzene silyloxies) that aliphatic group or aryl replace.
The acetal radical example comprises the group shown in the following general formula :-C (RR ')-OR " and-O-C (RR ')-OR ".Comprised methoxyl methyl, ethoxymethyl, the third oxygen methyl, fourth oxygen methyl, the different third oxygen methyl, uncle's fourth oxygen methyl and new penta oxygen methyl by the example of the group shown in the previous general formula.Comprised methoxy methoxy base, ethoxy methoxyl group, the third oxygen methoxyl group, the different third oxygen methoxyl group, positive fourth oxygen methoxyl group, uncle's fourth oxygen methoxyl group and positive penta oxygen methoxyl group, just own oxygen methoxyl group, ring penta oxygen methoxyl group and hexamethylene oxygen methoxyl group by the example of the group shown in the back general formula.
R
1, R
2And R
3Each is alkoxyl group preferably all, is more preferably methoxyl group.Consequently, the dispersiveness of weighting agent can improve.
In the compound shown in the above-mentioned formula (1), R
4And R
5Be same or different, each in them is all represented hydrogen atom, alkyl or cyclic ethers base.
Be used for R
4And R
5Alkyl can be exemplified as alkyl same as described above.
Be used for R
4And R
5The example of cyclic ethers base comprise: the cyclic ethers base with an ehter bond is Oxyranyle, oxetanyl, tetrahydrofuran (THF) (oxolane) base, Oxyranyle, oxepane (oxepane) base, oxocane base, oxonane base, oxecane (oxecane) base, trimethylene oxide (oxete) base, oxole base for example; Cyclic ethers base with two ehter bonds is dioxolanyl, dioxane base, Dioxepane (dioxepane) base and dioxane decane (dioxecane) base for example; Cyclic ethers base with three ehter bonds is the trioxane base for example.In these examples, has the C of an ehter bond
2-7The cyclic ethers base is preferred, has the C of an ehter bond
3-5The cyclic ethers base is more preferably.Cyclic ether group does not preferably contain unsaturated link(age) in ring structure.
R
4And R
5Each is preferred alkyl (preferred C all
1-3, be more preferably C
1-2), be more preferably ethyl.Consequently, the dispersiveness of weighting agent can improve.
N (integer) preferred 2 to 5.N in this scope can improve the dispersiveness of weighting agent.N is more preferably 2 to 4, and most preferably 3.If n is below 1, modified-reaction may be suppressed.If n is more than 6, modified effect may weaken.
The object lesson of the compound shown in the above-mentioned formula (1) comprises:
3-aminopropyl dimethyl methyl oxosilane,
3-aminopropyl methyl dimethoxy oxosilane,
3-aminopropyl ethyl dimethoxy silane,
The 3-aminopropyl trimethoxysilane,
3-aminopropyl dimethylethoxysilane,
3-aminopropyl methyldiethoxysilane,
The 3-aminopropyl triethoxysilane,
3-aminopropyl dimethyl butyrate TMOS,
3-aminopropyl methyl dibutoxy silane,
The dimethylaminomethyl Trimethoxy silane,
2-dimethylaminoethyl Trimethoxy silane,
3-dimethyl aminopropyl Trimethoxy silane,
4-dimethylamino butyl trimethoxy silane,
Dimethylaminomethyl dimethoxy-methyl silane,
2-dimethylaminoethyl dimethoxy-methyl silane,
3-dimethyl aminopropyl dimethoxy-methyl silane,
4-dimethylamino butyl dimethoxy-methyl silane,
The dimethylaminomethyl triethoxyl silane,
2-dimethylaminoethyl triethoxyl silane,
3-dimethyl aminopropyl triethoxyl silane,
4-dimethylamino butyl triethoxyl silane,
Dimethylaminomethyl diethoxymethyl silane,
2-dimethylaminoethyl diethoxymethyl silane,
3-dimethyl aminopropyl diethoxymethyl silane,
4-dimethylamino butyl diethoxymethyl silane,
The diethyl amino methyltrimethoxy silane,
2-diethyl aminoethyl Trimethoxy silane,
3-diethyl amino propyl trimethoxy silicane,
4-diethyl amino butyl trimethoxy silane,
Diethyl amino methyl dimethoxy oxygen ylmethyl silane,
2-diethyl aminoethyl dimethoxy-methyl silane,
3-diethyl amino propyl group dimethoxy-methyl silane,
4-diethyl amino butyl dimethoxy-methyl silane,
The diethyl amino Union carbide A-162,
2-diethyl aminoethyl triethoxyl silane,
3-diethyl amino propyl-triethoxysilicane,
4-diethyl amino butyl triethoxyl silane,
Diethyl amino methyl diethoxymethyl silane,
2-diethyl aminoethyl diethoxymethyl silane,
3-diethyl amino propyl group diethoxymethyl silane,
4-diethyl amino butyl diethoxymethyl silane; And by the compound shown in the following formula (4) to (11).In these compounds each can be used alone, and use perhaps can be combined more than two in them.In the middle of these compounds, 3-diethyl amino propyl trimethoxy silicane, 3-dimethyl aminopropyl Trimethoxy silane and be preferred by the compound shown in the following formula (4) are because weighting agent can have better dispersiveness.
About by method, can use for example disclosed method in JP H6-53768B, JP H6-57767B and JP 2003-514078T of common known method with compound (properties-correcting agent) the modification divinyl rubber shown in the above-mentioned formula (1).Modification is needed to be to make divinyl rubber contact with properties-correcting agent, and for example a kind of method is to form divinyl rubber by polymerization, and the properties-correcting agent with predetermined amount is added in the emulsion polymerized rubber solution then; The another kind of method that can adopt is that properties-correcting agent is added in the divinyl rubber solution so that they are reacted mutually.
The BR that is modified can be exemplified as BR same as described above.
The suitable example of BR comprises with rare earth catalyst synthetic divinyl rubber (being called " rare earth BR ").When the rare earth BR with high-cis content and low vinyl content used with HPNR, the wear resistance that can guarantee was so that can successfully obtain effect of the present invention.As rare earth catalyst, can use known those.Its example comprises the catalyzer that contains group of the lanthanides row rare earth compound, organo-aluminium compound, aikyiaiurnirsoxan beta (aluminoxanes), perhaps comprises the catalyzer of halogen compounds, preferred Lewis base.In these compounds, especially preferably comprise and contain the Nd catalyzer of neodymium (Nd) compound as group of the lanthanides row rare earth compound.
The example of group of the lanthanides row rare earth compound comprises halogenide, carboxylate salt, ethylate, sulfo-alcoholate (thioalcoholates) and the acid amides of the rare earth metal with ordination number 57-71.As mentioned above, the Nd catalyzer is preferred, because can obtain having the BR of high-cis content and low vinyl content.
As organo-aluminium compound, can use to be expressed as AlR
aR
bR
cCompound (R wherein
a, R
bAnd R
cBe identical or different, each in them is represented hydrogen or C
1-8Alkyl).The aikyiaiurnirsoxan beta example comprises straight chain aikyiaiurnirsoxan beta and ring-type aikyiaiurnirsoxan beta.The example that contains the compound of halogen comprises: be expressed as AlX
kR
d 3-KAluminum halide (wherein X represents halogen, R
dRepresent C
1-20Alkyl, aryl or aralkyl, and K represents 1,1.5,2 or 3); Strontium halogenide is Me for example
3SrCl, Me
2SrCl
2, MeSrHCl
2And MeSrCl
3And metal halide for example first silicon chlorides, tin tetrachloride and titanium tetrachloride.Lewis base can be used to complexing group of the lanthanides row rare earth compound, and its suitable examples comprises methyl ethyl diketone, ketone and alcohols.
In the polymerization of divinyl, the solution that rare earth catalyst can be used as in the organic solvent (for example normal hexane, hexanaphthene, normal heptane, toluene, dimethylbenzene or benzene) is used, perhaps by for example silicon-dioxide, magnesium oxide or the magnesium chloride carrying of a kind of appropriate carriers.And polymerizing condition can adopt solution polymerization or mass polymerization.Polymerization temperature is preferably at-30 to 150 ℃, and polymerization pressure can depend on that other conditions are suitably set.
The mooney viscosity ML of rare earth BR
1+4(100 ℃) are preferred more than 35, and are more preferably more than 40, further preferred more than 44.Mooney viscosity less than 35 may cause the unvulcanized rubber composition have low viscosity and may not guarantee to vulcanize after suitable thickness.The mooney viscosity of rare earth BR is preferred below 55, is more preferably below 50.If mooney viscosity surpasses 55, be difficult to be extruded and level and smooth edge is provided to such an extent as to the unvulcanized rubber composition may become very hard.
Mooney viscosity is measured according to ISO289 and JIS K6300.
The ratio (Mw/Mn) that rare earth BR weight-average molecular weight (Mw) is compared number-average molecular weight (Mn) preferably more than 1.2, is more preferably more than 1.5, and is further preferred more than 2.5.If Mw/Mn is less than 1.2, then workability has the tendency of remarkable deterioration.Mw/Mn preferably below 5, is more preferably below 4, and is further preferred below 3.If Mw/Mn surpasses 5, then wear resistance may seldom be enhanced.
The Mw of rare earth BR preferably more than 300000, is more preferably more than 500000, and is further preferred more than 550000.Mw is preferred below 1500000, and more preferably below 1200000.The Mn of rare earth BR preferably more than 100000, is more preferably more than 150000.Mn is preferred below 1000000, and more preferably below 800000.If Mw or Mn are less than its minimum value, then wear resistance and fuel economy tend to reduce.If Mw or Mn surpass its maximum value, workability may worsen.
In the present invention, Mw and Mn by gel dialysis chromatography (GPC) with respect to polystyrene standard and determined.
The cis-content of rare earth BR preferably more than the 95 quality %, is more preferably more than the 96 quality %, further more than the preferred 97 quality %.If less than 95 quality %, then wear resistance may seldom be enhanced.The upper limit of the cis-content of rare earth BR is not particularly limited, and can be 100 quality %.
The contents of ethylene of rare earth BR preferably below the 1.0 quality %, is more preferably below the 0.8 quality %, further below the preferred 0.6 quality %, and below the preferred especially 0.5 quality %.If contents of ethylene surpasses 1.0 quality %, then wear resistance may seldom be enhanced.The lower limit of the contents of ethylene of rare earth BR is not particularly limited, and can be 0 quality %.
In the present invention, the contents of ethylene of rare earth BR (1, the content of 2-key butadiene unit) and cis-content (cis-1, the content of 4-key butadiene unit) can be measured by infrared absorption spectrum analysis.
The content of BR in 100 quality % rubber components (BR and the rare earth BR that comprise modification) is more than the 5 quality %, more than the preferred 8 quality %.If content is less than 5 quality %, then wear resistance may not can be substantially improved.The content of BR is below the 40 quality % in 100 quality % rubber components, below the preferred 35 quality %, is more preferably below the 32 quality %.If content surpasses 40 quality %, then the relative proportion of HPNR reduces, and fuel economy has the tendency of deterioration.
The total content of HPNR and BR preferably more than the 70 quality %, is more preferably more than the 80 quality % in 100 quality % rubber components, more than the further preferred 90 quality %, and preferred especially 100 quality %.If total content is less than 70 quality %, each performance may not balancedly reach.
Be used for rubber example of the present invention in addition and comprise elastoprene for example natural rubber (NR), synthetic polyisoprene (IR), styrene-butadiene rubber(SBR) (SBR), paracril (NBR), neoprene (CR) and isoprene-isobutylene rubber (IIR).
Rubber combination of the present invention preferably comprises silicon-dioxide.Comprise silicon-dioxide and make and to improve enhancing property and fuel economy, so that can successfully obtain effect of the present invention.The example of silicon-dioxide comprises dry method silicon-dioxide (dehydrate of silicon) and wet method silicon-dioxide (aqueous silicic acid).Wet method silicon-dioxide is preferred, because it has more silanol group.
The average primary particle diameter of silicon-dioxide preferably more than the 10nm, is more preferably more than the 15nm.If average primary particle diameter is less than 10nm, then silicon-dioxide may seldom be disperseed, and fuel economy and workability are tended to worsen.The average primary particle diameter of silicon-dioxide preferably below the 40nm, is more preferably below the 30nm.If average primary particle diameter is greater than 40nm, rubbery intensity tends to variation, and wear resistance is tended to worsen.
The silicon-dioxide average primary particle diameter can be by measuring with electron microscope observation silicon-dioxide, measures its any 50 particle grain size and get the mean value of particle diameter.
Nitrogen adsorption specific surface area (the N of silicon-dioxide
2SA) preferred 120m
2More than/the g, be more preferably 140m
2More than/the g, further preferred 150m
2More than/the g.If N
2SA is less than 120m
2/ g then has to obtain enough tendencies of enhancing property.The N of silicon-dioxide
2SA is 250m preferably
2Below/the g, be more preferably 200m
2Below/the g.If N
2SA is greater than 250m
2/ g, then the unvulcanized rubber composition viscosity tends to increase and workability is tended to worsen.
The N of silicon-dioxide
2SA measures by the BET method according to ASTM D3037-81.
Based on per 100 mass parts rubber components, the content of silicon-dioxide is more than 10 mass parts, more than preferred 12 mass parts.If the content of silicon-dioxide is less than 10 mass parts, then the effect of being brought by silicon-dioxide has the tendency of insufficient embodiment.Based on per 100 mass parts rubber components, the content of silicon-dioxide is below 60 mass parts, below preferred 45 mass parts, is more preferably below 35 mass parts.If the content of silicon-dioxide is greater than 60 mass parts, then the unvulcanized rubber composition viscosity tends to increase and workability is tended to worsen.
Rubber compound of the present invention can comprise silane coupling agent, and this silane coupling agent is the multipolymer that comprises unit B shown in unit A shown in the above-mentioned formula (2) and the above-mentioned formula (3), and wherein to account for the ratio of unit A and unit B mole total amount be 1 to 70mol% to unit B.When rubber compound comprises the silane coupling agent with said structure,, just can reach good silicon-dioxide dispersiveness with HPNR and BR (preferred rare earth BR).Therefore, fuel economy and wear resistance also can improve, and processibility also is guaranteed simultaneously.
In having the silane coupling agent of said structure, the molar ratio of unit A and unit B satisfies aforementioned condition.Therefore, with polysulphide silane for example two (3-triethoxysilylpropyl) tetrasulfide compare, the viscosity that this silane coupling agent has suppressed after the processing increases.Can imagine owing to following reason: because the sulfuration of unit A partly is the C-S-C key, compare with tetrasulfide or disulphide, the sulfuration part has thermostability.Therefore, the increase of mooney viscosity is less.
If the molar ratio of unit A and unit B satisfies this condition, to compare with hydrosulphonyl silane (as the 3-mercaptopropyltriethoxysilane), silane coupling agent has suppressed the minimizing of scorch time.Can imagine owing to following reason: unit B has the hydrosulphonyl silane structure, among the unit A-C
7H
15Part has covered in the unit B-the SH group.Therefore ,-the SH group is unlikely to react with polymkeric substance.Thereby, the unlikely minimizing of scorch time, the also unlikely increase of viscosity.
Be used for R
6The example of halogen comprise chlorine, bromine and fluorine.
Be used for R
6And R
7Side chain or unbranched C
1-30The example of alkyl comprises methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl group, nonyl, decyl.Alkyl carbon atoms number preferably 1 to 12.
Be used for R
6And R
7Side chain or unbranched C
1-30The example of alkylidene group comprises ethylidene, propylidene, butylidene, pentylidene, hexylidene, inferior heptyl, octylene, nonamethylene, inferior decyl, inferior undecyl, inferior dodecyl, inferior tridecyl, inferior tetradecyl, inferior pentadecyl, inferior hexadecyl, inferior heptadecyl and inferior octadecyl.Alkylidene group carbonatoms preferably 1 to 12.
Be used for R
6And R
7Side chain or unbranched C
2-30The example of alkenyl comprises vinyl, 1-propenyl, 2-propenyl, 1-butylene base, crotyl, 1-pentenyl, pentenyl, 1-hexenyl, 2-hexenyl and 1-octenyl.Alkenyl carbonatoms preferably 2 to 12.
Be used for R
6And R
7Side chain or unbranched C
2-30The example of alkylene group comprises vinylidene, 1-propenylidene, 2-propenylidene, 1-crotonylidene, 2-crotonylidene, 1-inferior pentenyl, 2-inferior pentenyl, the inferior hexenyl of 1-, the inferior hexenyl of 2-and the inferior octenyl of 1-.Alkylene group carbonatoms preferably 2 to 12.
Be used for R
6And R
7Side chain or unbranched C
2-30The example of alkynyl comprises ethynyl, proyl, butynyl, pentynyl, hexin base, heptyne base and octyne base.Alkynyl carbonatoms preferably 2 to 12.
Be used for R
6And R
7Side chain or unbranched C
2-30The example of alkynylene comprises ethynylene, inferior proyl, butynelene, inferior pentynyl, inferior hexin base, inferior heptyne base, inferior octyne base, inferior n-heptylacetylene base, inferior decynyl, inferior undecyne base, inferior dodecyne base.Carbon number in the alkynylene preferred 2 to 12.
In having the silane coupling agent of said structure, the repetition sum (x+y) of the repeat number (y) of the repeat number of unit A (x) and unit B preferably 3 to 300.If the sum in this scope, then among the unit A-C
7H
15But the hydrosulphonyl silane (mercaptosilan) among the part capping unit B.Therefore, can suppress the minimizing of scorch time, and simultaneously can assurance and the better reactive behavior of silicon-dioxide and rubber components.
Silane coupling agent example with said structure comprises NXT-Z30, NXT-Z45 and NXT-Z60 (all being produced by MomentivePerformanceMaterials).These silane coupling agents can use separately, and perhaps they can be used in combination more than both.
Based on per 100 mass parts silicon-dioxide, the content of silane coupling agent with said structure is more preferably more than 4 mass parts, further more than preferred 6 mass parts preferably more than 2 mass parts.If content is less than 2 mass parts, thereby then rolling resistance is tended to increase fuel economy and is tended to worsen.Based on per 100 mass parts silicon-dioxide, the content of silane coupling agent preferably below 20 mass parts, is more preferably below 16 mass parts, further below preferred 12 mass parts, below preferred especially 10 mass parts.If content surpasses 20 mass parts, then the effect of Huo Deing tends to be unworthy increasing cost.
Rubber combination can randomly comprise the food ingredient that is generally used for rubber industry except that mentioned component.The example of food ingredient comprises for example for example sulphur and sulfocompound and vulcanization accelerator of carbon black, oils or softening agent, antioxidant, antiaging agent, zinc oxide, vulcanizing agent of weighting agent.
Rubber combination of the present invention preferably comprises carbon black.Available sooty example includes, but are not limited to, GPF, FEF, HAF, ISAF and SAF.If rubber combination comprises carbon black, can improve enhancing.Therefore, it can successfully obtain effect of the present invention with being used in combination of HPNR and BR.
Sooty nitrogen adsorption specific surface area (N
2SA) preferred 20m
2More than/the g, be more preferably 35m
2More than/the g, further preferred 70m
2More than/the g, preferred especially 100m
2More than/the g.If N
2SA is less than 20m
2/ g quality then may not obtain enough enhancings.Sooty N
2SA is 200m preferably
2Below/the g, be more preferably 150m
2Below/the g.If N
2SA is greater than 200m
2/ g, the unlikely quilt of carbon black successfully disperses.
Sooty nitrogen adsorption specific surface area is measured according to JIS K6217 method.
Comprise in the sooty situation at rubber combination, based on per 100 mass parts rubber components, more than preferred 5 mass parts of sooty content, be more preferably more than 10 mass parts, further more than preferred 15 mass parts, more than preferred especially 20 mass parts, most preferably more than 30 mass parts.If content is less than 5 mass parts, then enhancing property may not can be substantially improved.Based on per 100 mass parts rubber components, below preferred 100 mass parts of sooty content, be more preferably below 80 mass parts, further below preferred 60 mass parts, below preferred especially 45 mass parts, most preferably below 40 mass parts.If content surpasses 100 mass parts, then the unlikely quilt of carbon black successfully disperses.In addition, the workability trend worsens.
In rubber combination of the present invention, based on per 100 mass parts rubber components, the total content of carbon black and silicon-dioxide preferably more than 15 mass parts, is more preferably more than 30 mass parts, further more than preferred 45 mass parts.Based on per 100 mass parts rubber components, this total content preferably below 100 mass parts, is more preferably below 80 mass parts, further below preferred 65 mass parts, below preferred especially 55 mass parts.If total content in this scope, can reach wear resistance preferably.In rubber combination of the present invention, because be used in combination the HPNR and the BR of predetermined amount, can reach fuel economy preferably, do not reduce the total content of carbon black and silicon-dioxide.
In rubber combination of the present invention, based on per 100 mass parts rubber components, oils content preferably below 5 mass parts, is more preferably below 1 mass parts, further preferred 0 mass parts (not having oils basically).In rubber combination of the present invention, compare with using NR, use HPNR that mooney viscosity is reduced.Therefore, keeping the workability while preferably, the content of oils can be lowered, thereby further improves fuel economy.
Rubber combination of the present invention is by common method production.More particularly, rubber combination is such as by comprising with mixer instance such as Banbury mixer, kneader or mill mixing mentioned component, vulcanizes the method that generates mixture then and produces.Rubber combination of the present invention is applicable to the tyre surface (crown (cap tread)) of heavy duty tire (in particular for truck and motorbus) tire.
Heavy duty tire of the present invention is produced with above-mentioned rubber combination by the method for routine.More particularly, to comprise the unvulcanized rubber composition extruding of mentioned component and be processed into the shape of tire integral part such as tyre surface, mode with routine is molded on building machine with other tire integral part then, so that form unvulcanized tire.Then, unvulcanized tire is heated pressurization in vulcanizing apparatus, so that generate heavy duty tire of the present invention.
Embodiment
To describe the embodiment of the invention particularly below, but the present invention is not limited thereto.
The various chemical reagent that are used for embodiment 1 to 4 and comparative example 1 to 3 are listed in as follows.
Natural rubber latex: from the fresh latex of Thaitex company acquisition
Tensio-active agent: the Emal-E that Kao Corp produces
NaOH: the NaOH that Wako Pure Chemical Industries, Ltd. produces
NR：TSR
HPNR (saponification natural rubber): following goods 1
Unmodified BR: the BR 150B that Ube Industries, Ltd produces
Modification BR: modification divinyl rubber (S-modification BR (terminal-modified), contents of ethylene: 15 quality %, R that Sumitomo Chemical Co produces
1, R
2, R
3=-CH
2CH
3N=3)
Carbon black: the SHOBLACK N220 (N that CABOT JAPAN K.K. Corp. produces
2SA:111m
2/ g)
Wax: the Sunnoc wax that the emerging chemical industry of imperial palace Co., Ltd. produces
Antiaging agent: the antiaging agent 6C (SANTOFLEX 6PPD) that Flexsys Inc. (FLEXSYS) produces
Stearic acid: the stearic acid " TSUBAKI " that NOF Corp (NOF Corporation) produces
Zinc oxide: the zinc oxide #2 that Mitsui mining industry Co., Ltd. produces
Sulphur: crane sees the Sulfur powder that chemical industry Co., Ltd. produces
Vulcanization accelerator: the Nocceler NS that the emerging chemical industry pillar of imperial palace commercial firm produces
(with the preparation of alkali saponified natural rubber)
Goods 1
The solids content of natural rubber latex (DRC) is adjusted to 30% (w/v).And then, the 1000g natural rubber latex is mixed with 10g Emal-E and 20g NaOH, saponification at room temperature is 48 hours then.Produce a kind of saponification natural rubber latex whereby.The DRC of dilute with water saponification latex to 15% (w/v).The latex of dilution is mixed with formic acid, slowly stir simultaneously, so that pH is adjusted to 4.0-4.5.Latex solidifies, and the rubber that solidifies is broken and use the 1000ml water washing.Descended dry two hours at 110 ℃ then, obtain solid rubber (saponification natural rubber) whereby.
The TSR and the solid rubber that produce in the goods 1 are measured nitrogen content, phosphorus content and gel content by the following method.Table 1 has shown the result.
(mensuration of nitrogen content)
Measure nitrogen content with CHN CORDER MT-5 (production of Yanaco analytical instrument company).In mensuration, at first by formulating the working curve that is used for determining nitrogen content as reference material with quinizine.Then, weigh the modified natural rubber that produces in the TSR sample of about 10mg or the goods 1 and measuring.By three measurement result calculating mean values, and got the nitrogen content of making sample.
(mensuration of phosphorus content)
(ICPS-8100, Shimadzu Corporation produces) measures phosphorus content with the ICP emission spectrometer.
Phosphorus
31P-NMR measures and also can carry out as follows: the composition that extracts from untreated rubber with chloroform is purified, and is dissolved in then among the CDCl3 so that the preparation test sample.Based on measuring the standard (0ppm) of peak value, with nuclear magnetic resonance spectrometer (Bruker Japanese firm produces for 400 megahertzes, AV 400M) analytical test sample corresponding to phosphorus atom in 80% phosphate aqueous solution.
(mensuration of gel content)
Weighing is cut into the untreated rubber sample of 1mm * 1mm size, each 70.00mg, mixes with 35ml toluene, and leaves standstill a week in cold and dark place.And then, mixture so that be settled out the gel component of insoluble toluene, and is removed the supernatant liquor that dissolves in toluene by centrifugal.Gel component is solidified with methyl alcohol individually and is dry then.Measure the quality of exsiccant gel component, determine gel content (%) with following formula then.
Gel content (quality %)=[quality (mg) of the quality of xerogel component (mg)/primary sample] * 100
Table 1
| Saponification natural rubber (goods 1) | TSR | |
| Nitrogen content (quality %) | ?0.12 | 0.33 |
| Phosphorus content (ppm) | ?84 | 572 |
| Gel content (quality %) | ?5.5 | 26.9 |
As shown in table 1, to find to compare with TSR, saponification natural rubber (HPNR) has nitrogen content, phosphorus content and the gel content of minimizing.In addition, the modified natural rubber that produces in the goods 1 shows that the extracting solution that does not have corresponding to it exists
31Phosphatide peak in the P-NMR spectrum between-3ppm and 1ppm.
＜embodiment 1 to 4 and comparative example 1 to 3 〉
Each prescription according to shown in the table 2 will mix so that obtain mixture by the 1.7-L Banbury mixer except the chemical reagent sulphur and the vulcanization accelerator.And then, sulphur and vulcanization accelerator are added in the mixture of generation, and they are mixed in mill.Produce the unvulcanized rubber composition whereby.The unvulcanized rubber composition that generates pressurizeed 30 minutes at 150 ℃ with the thick mould of 2mm.Produce vulcanizate compositions whereby.
The vulcanizate compositions that generates is tested with following manner.
(heating index)
Measure the tan δ of each vulcanizate compositions under the following conditions with a kind of visco-elasticity spectrometer VES (production of Co., Ltd. of this making of rock institute): 70 ℃ of temperature; Initial strain 10%; Dynamic strain 2%.Tan δ value representation with respect to comparative example 1 is 100, by following formula the tan δ of each prescription is expressed as index value.Index is more little, means that heating is few more, and promptly fuel economy is good more.
(heating index)=(the Tan δ of each prescription)/(the Tan δ of comparative example 1) * 100
(abrasion resistance index)
Measure the Lambourn abrasion loss of each vulcanizate compositions under the following conditions with a kind of Lambourn abrasion tester (production of Co., Ltd. of this making of rock institute): surperficial speed of rotation 50m/min; Applied load 3.0kg; Dirt powder dropleting speed (dropping rate) 15g/min; Slip ratio 20%.Calculate VOLUME LOSS by the Lambourn abrasion loss of measuring then.Value representation with respect to the VOLUME LOSS of comparative example 1 is 100, by following formula the VOLUME LOSS of each prescription is expressed as index value.Index is big more, means that wear resistance is good more.
(abrasion resistance index)=(VOLUME LOSS of comparative example 1)/(VOLUME LOSS of each prescription) * 100
(degradation resistant)
The thermal destruction seven days in 80 ℃ baking oven of each vulcanizate compositions is so that obtain the sample of degrading.Make the degraded sample stand tension test according to JIS K6251 then, so that the extension at break of working sample.Value representation with respect to the extension at break of comparative example 1 is 100, by following formula the extension at break of each prescription is expressed as index value.Index is big more, means that degradation resistant is good more.
(degradation resistant index)=(extension at break of each prescription)/(extension at break of comparative example 1) * 100
Table 2
Table 2 shows, in the embodiment that HPNR and BR are used in combination, obtains high-caliber fuel economy and wear resistance in better equilibrated mode, keeps good degradation resistant simultaneously.Especially, in the embodiment 4 that uses modification BR, obtained fabulous performance.On the other hand, in the comparative example 1 and 2 that is not used in combination HPNR and BR and the content of HPNR and BR exceed in the comparative example 3 outside the pre-determined range separately, performance is not as the performance among the embodiment.
Hereinafter, the various chemical reagent that are used for embodiment 5 to 13 and comparative example 4 and 5 are listed in as follows.
NR：TSR
HPNR (saponification natural rubber): above-mentioned goods 1
Co BR1: the BR 150B that Ube Industries, Ltd produces is (with Co catalyzer synthetic BR, cis-content: 97.0 quality %, contents of ethylene: 1.5 quality %, ML
1+4(100 ℃): 40, Mw:52.0 * 10
4, Mn:15.0 * 10
4, Mw/Mn:3.3)
Co BR2: the BR 150L that Ube Industries, Ltd produces is (with Co catalyzer synthetic BR, cis-content: 98.2 quality %, contents of ethylene: 1.0 quality %, ML
1+4(100 ℃): 43, Mw:54.2 * 10
4, Mn:22.1 * 10
4, Mw/Mn:2.4)
Nd BR: the Buna CB 24 that Lanxess Corporation (LANXESS) produces is (with Nd catalyzer synthetic BR, cis-content: 97.6 quality %, contents of ethylene: 0.4 quality %, ML
1+4(100 ℃): 45, Mw:59.7 * 10
4, Mn:22.2 * 10
4, Mw/Mn:2.7)
Carbon black: the SHOBLACK N220 (N that Cabot Japan K.K. Corp. produces
2SA:111m
2/ g)
Silicon-dioxide: ULTRASIL VN3 (average primary particle diameter: 15nm, N that Degussa company (Degussa AG) produces
2SA:175m
2/ g)
Silane coupling agent 1: the Si266 (sulfide silane) that Degussa company (Degussa AG) produces
Silane coupling agent 2: the A1891 (hydrosulphonyl silane) that MomentivePerformanceMaterials (Momentive Performance Materials) produces
Silane coupling agent 3: the NXT-Z45 (multipolymer of unit A and unit B (unit A:55mol%, unit B: 45mol%)) that MomentivePerformanceMaterials (Momentive Performance Materials) produces
Silane coupling agent 4: the NXT-Z15 (multipolymer of unit A and unit B (unit A:85mol%, unit B: 15mol%)) that MomentivePerformanceMaterials (Momentive Performance Materials) produces
Silane coupling agent 5: the NXT-Z60 (multipolymer of unit A and unit B (unit A:40mol%, unit B: 60mol%)) that MomentivePerformanceMaterials (Momentive Performance Materials) produces
Wax: the Sunnoc wax that the emerging chemical industry pillar of imperial palace commercial firm produces
Antiaging agent: the antiaging agent 6C (SANTOFLEX 6PPD) that Flexsys Inc. (FLEXSYS) produces
Stearic acid: the stearic acid " TSUBAKI " that NOF Corp (NOF Corporation) produces
Zinc oxide: the zinc oxide #2 that Mitsui mining industry Co., Ltd. produces
Sulphur: crane sees the Sulfur powder that chemical industry Co., Ltd. produces
Vulcanization accelerator: the Nocceler NS that the emerging chemical industry pillar of imperial palace commercial firm produces
＜embodiment 5 to 13 and comparative example 4 and 5 〉
Each prescription according to shown in table 3 and 4 will mix by the 1.7-L Banbury mixer except the chemical reagent sulphur and the vulcanization accelerator, so that obtain mixture.And then, sulphur and vulcanization accelerator are added in the mixture of generation, and they are mixed in mill.Produce the unvulcanized rubber composition whereby.The unvulcanized rubber composition that generates pressurizeed 30 minutes at 150 ℃ with the thick mould of 2mm.Produce vulcanizate compositions whereby.
The unvulcanized rubber composition and the vulcanizate compositions that generate are tested with following manner.
(heating index)
Measure the tan δ of each vulcanizate compositions under the following conditions with a kind of visco-elasticity spectrometer VES (production of Co., Ltd. of this making of rock institute): 70 ℃ of temperature; Initial strain 10%; Dynamic strain 2%.Value representation with respect to the tan δ of comparative example 5 is 100, by following formula the tan δ of each prescription is expressed as index value.Index is more little, means that heating is few more, and promptly fuel economy is good more.
(heating index)=(the Tan δ of each prescription)/(the Tan δ of comparative example 5) * 100
(abrasion resistance index)
Measure the Lambourn abrasion loss of each vulcanizate compositions under the following conditions with a kind of Lambourn abrasion tester (production of Co., Ltd. of this making of rock institute): surperficial speed of rotation 50m/min; Applied load 3.0kg; Dirt powder dropleting speed 15g/min; Slip ratio 20%.Calculate VOLUME LOSS by the Lambourn abrasion loss of measuring then.Value representation with respect to the VOLUME LOSS of comparative example 5 is 100, by following formula the VOLUME LOSS of each prescription is expressed as index value.Index is big more, means that wear resistance is good more.
(abrasion resistance index)=(VOLUME LOSS of comparative example 5)/(VOLUME LOSS of each prescription) * 100
(mooney viscosity index)
Under 100 ℃, measure the mooney viscosity of each unvulcanized rubber composition according to JIS K6300.Value representation with respect to the mooney viscosity of comparative example 5 is 100, by following formula the mooney viscosity of each prescription is represented as index value.Index is big more, means that mooney viscosity is low more, and promptly workability is good more.
(mooney viscosity index)=(mooney viscosity of comparative example 5)/(mooney viscosity of each prescription) * 100
(scorch time index)
Under 160 ℃, measure each unvulcanized rubber composition and will reach the needed time (T of 10% sulphidity according to JIS K6300
10).T with respect to comparative example 5
10Value representation is 100, according to following formula the measuring result of each prescription is expressed as index value.Index is big more, means that scorch time is long more, and promptly workability is good more.
(scorch time index)=(T of each prescription
10The T of)/(comparative example 5
10) * 100
Table 3
Table 4
Table 3 and table 4 show, are being used in combination HPNR, Nd BR and silicon-dioxide and are using among the embodiment any in the silane coupling agent 3 to 5, and the equilibrium that has obtained fuel economy and wear resistance with high level improves.In addition, workability is good, and has reached these performances in well balanced mode.On the other hand, mentioned component is not combined the performance of the comparative example that uses not as the performance of embodiment.
Claims (13)
1. rubber composition for tire, it comprises:
Rubber components, it comprises phosphorus content is following modified natural rubber and divinyl rubber of 200ppm,
Wherein, be benchmark with the rubber components of 100 quality %, the content of described modified natural rubber is 60-95 quality %, the content of described divinyl rubber is 5-40 quality %.
2. rubber composition for tire as claimed in claim 1 is characterized in that, the gel content of described modified natural rubber is that described gel content is confirmed as being insoluble to the substances content of toluene below the 20 quality %.
3. rubber composition for tire as claimed in claim 1 is characterized in that, described modified natural rubber is to its chloroform extract
31During P NMR measures, in-3 to 1ppm scopes, there is not the phosphatide peak, so that it does not contain phosphatide substantially.
4. rubber composition for tire as claimed in claim 1 is characterized in that, described modified natural rubber comprises the following nitrogen of 0.3 quality %.
5. rubber composition for tire as claimed in claim 1 is characterized in that, described modified natural rubber is produced by the saponification natural rubber latex.
6. rubber composition for tire as claimed in claim 1 is characterized in that, described divinyl rubber is the modification divinyl rubber.
7. rubber composition for tire as claimed in claim 6 is characterized in that, described divinyl rubber compound modified by shown in the formula (1):
R wherein
1, R
2And R
3Be same or different, each in them is all represented alkyl, alkoxyl group, silyloxy, acetal radical, carboxyl, sulfydryl or their derivative,
R
4And R
5Be same or different, each in them is all represented hydrogen atom, alkyl or cyclic ethers base, and
N represents integer.
8. rubber composition for tire as claimed in claim 1 is characterized in that, described divinyl rubber is to use the rare earth catalyst synthetic.
9. rubber combination as claimed in claim 8 is characterized in that, described cis-content with rare earth catalyst synthetic divinyl rubber is more than the 95 quality %, and the content of vinyl is below the 1.0 quality %.
10. rubber combination as claimed in claim 1 further comprises:
Silicon-dioxide and
Silane coupling agent,
Wherein said silane coupling agent is the multipolymer that comprises the unit B shown in unit A shown in the formula (2) and the formula (3), and the ratio that unit B accounts for unit A and unit B integral molar quantity is 1 to 70 mole of %, and
Based on per 100 mass parts rubber components, the amount of silicon-dioxide is 10 to 60 mass parts:
Wherein, each is integer more than 1 for x and y, R
6Represent hydrogen, halogen, side chain or unbranched C
1-30Alkyl or alkylidene group, side chain or unbranched C
2-30Alkenyl or alkylene group, side chain or unbranched C
2-30Alkynyl or alkynylene or the group that obtains by terminal hydrogen with hydroxyl or carboxyl substituted alkyl or alkenyl,
R
7Represent hydrogen, side chain or unbranched C
1-30Alkylidene group or alkyl, side chain or unbranched C
2-30Alkylene group or alkenyl or side chain or unbranched C
2-30Alkynylene or alkynyl, and
R
6And R
7Can form ring texture together.
11. rubber composition for tire as claimed in claim 1 is characterized in that, further comprises carbon black.
12. rubber composition for tire as claimed in claim 1 is characterized in that, described rubber combination is used to the tyre surface of heavy duty tire.
13. a heavy duty tire, it comprises the tyre surface by the described rubber combination preparation of claim 1.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010061445A JP5123342B2 (en) | 2010-03-17 | 2010-03-17 | Tire rubber composition and heavy duty tire |
| JP2010-061445 | 2010-03-17 | ||
| JP2010105530A JP5216045B2 (en) | 2010-04-30 | 2010-04-30 | Tire rubber composition and heavy duty tire |
| JP2010-105530 | 2010-04-30 |
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|---|---|
| CN102190822A true CN102190822A (en) | 2011-09-21 |
| CN102190822B CN102190822B (en) | 2014-10-29 |
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| CN201110040445.9A Expired - Fee Related CN102190822B (en) | 2010-03-17 | 2011-02-12 | Tire rubber composition and heavy-load tire |
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| Country | Link |
|---|---|
| US (1) | US8163821B2 (en) |
| EP (1) | EP2366558B1 (en) |
| CN (1) | CN102190822B (en) |
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- 2011-03-16 US US13/048,914 patent/US8163821B2/en active Active
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| CN1832967A (en) * | 2003-08-04 | 2006-09-13 | 田中康之 | Deproteinized natural rubber, its composition and use thereof |
| EP2147951A1 (en) * | 2007-05-15 | 2010-01-27 | Sumitomo Rubber Industries, Ltd. | Rubber composition for tire and pneumatic tire |
| EP2151476A1 (en) * | 2007-05-22 | 2010-02-10 | Sumitomo Rubber Industries, Ltd. | Rubber composition for tire and pneumatic tire |
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| CN103814076A (en) * | 2011-09-26 | 2014-05-21 | 住友橡胶工业株式会社 | Rubber composition for tire, and pneumatic tire |
| CN103102548B (en) * | 2011-10-25 | 2016-08-17 | 住友橡胶工业株式会社 | Rubber composition and pneumatic tire for clinch apex |
| CN103102548A (en) * | 2011-10-25 | 2013-05-15 | 住友橡胶工业株式会社 | Rubber composition for clinch apex and pneumatic tire |
| CN103073766A (en) * | 2011-10-25 | 2013-05-01 | 住友橡胶工业株式会社 | Rubber composition for tire, and pneumatic tire |
| CN103205039A (en) * | 2012-01-16 | 2013-07-17 | 住友橡胶工业株式会社 | Masterbatch, Rubber Composition, And Pneumatic Tire |
| CN103387700A (en) * | 2012-05-09 | 2013-11-13 | 住友橡胶工业株式会社 | Rubber composition and pneumatic tire |
| CN103509209A (en) * | 2012-06-27 | 2014-01-15 | 住友橡胶工业株式会社 | Rubber composition for tire, and pneumatic tire |
| CN103923362A (en) * | 2013-01-10 | 2014-07-16 | 住友橡胶工业株式会社 | Composite And Method For Producing The Same, Rubber Composition, And Pneumatic Tire |
| CN106661830A (en) * | 2014-06-12 | 2017-05-10 | 米其林集团总公司 | Semi-finished product including a cable gummed in situ and encased in a calendering rubber composition |
| CN106661830B (en) * | 2014-06-12 | 2019-02-01 | 米其林集团总公司 | The semi-finished product of cable including rubber processing in situ and packet in calendered rubber composition |
| CN107735441A (en) * | 2015-06-18 | 2018-02-23 | 株式会社普利司通 | Vibration damping rubber composition and vibration-proof rubber |
| CN110087901A (en) * | 2016-12-20 | 2019-08-02 | 米其林集团总公司 | Rubber composition comprising specific rubber powder |
| CN110087901B (en) * | 2016-12-20 | 2021-04-02 | 米其林集团总公司 | Rubber composition comprising specific rubber powder |
| CN108864497A (en) * | 2017-05-09 | 2018-11-23 | 住友橡胶工业株式会社 | Tire tread and tire |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102190822B (en) | 2014-10-29 |
| EP2366558A1 (en) | 2011-09-21 |
| US8163821B2 (en) | 2012-04-24 |
| EP2366558B1 (en) | 2012-10-31 |
| US20110230613A1 (en) | 2011-09-22 |
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